陈智辉,吴幼青,吴诗勇,黄胜,陈大波,孙硕,顾嘉乐
CHEN Zhihui,WU Youqing,WU Shiyong,HUANG Sheng,CHEN Dabo,SUN Shuo,GU Jiale

• 1:华东理工大学能源化工系
• 2:杭州牛墨科技有限公司

摘要(Abstract)：

红柳林煤(HLL)经温和加氢液化(430℃)和炭化(410℃)得到的液化残渣(DCLR)与其他5种原料煤在实验室条件下配煤炼焦制备坩埚焦,有利于缓解优质炼焦煤短缺的现状,降低配煤炼焦的成本,有利于实现煤炭资源的综合利用。研究了原煤黏结指数,利用不同配比的煤样进行实验室坩埚焦的制备,分析了其焦炭成焦率、冷态强度和热态强度等性质,并提出配煤体系中加入DCLR的作用机理。结果表明:加入5%和10%的DCLR可分别替代12%和18%的优质炼焦煤,且得到的焦炭品质不变。DCLR加入量从5%增至10%时,焦炭的抗碎强度提升了1.20%,耐磨强度降低了1.04%,焦炭的热反应性提升了3%,反应后强度增加了2%;此外,DCLR的添加量不宜过高(<15%),这是因为DCLR的高活性和高含量的惰性组分使配合煤的黏结性下降。DCLR最佳的制备条件为:液化温度430℃、炭化温度410℃、1%碱式氧化铁催化剂,此时制备的DCLR的黏结性指数为68,黏结性较强,适合作为配煤炼焦的添加剂和黏结剂。DCLR和气煤(QM)相互作用可部分替代肥煤(FM),使中间相的流动度增加、配煤的熔融温度区间拓宽,体系中大量气体冲刷胶质层,使胶质体充分渗透到煤颗粒的孔道中,得到高强度的焦炭。焦化初期,DCLR和QM的相互作用对于焦化关键过程有一定的影响,焦炭的各向异性程度增加。
In this paper, direct coal liquefaction residue(DCLR)obtained by mild hydroliquefaction(430 ℃)and carbonization process(410 ℃)of Hongliulin(HLL)coal was blended with other five coals to prepare crucible coke under the laboratory conditions, which was beneficial to alleviate the shortage of high quality coking coal, reduce the cost of coking, and make the utilization use of coal resources. The adhesion index of raw coal was studied, crucible cokes were prepared by using coal samples with different proportions, and the coke yield, cold strength and thermal strength of cokes were analyzed. In addition, the mechanism of DCLR addition in coal blending system was proposed. The results show that adding 5% and 10% DCLR into coal blending system can replace 12% and 18% high caking property coals respectively with coke quality promised. When the DCLR ratio increases from 5% to 10%,the crushing strength increases about 1.20%,the abrasive resistance decreases about 1.04%,the coke reactivity index increases about 3% and the coke strength after reaction increases about 2%. In addition, the addition amount of DCLR should not be too high(<15%),because the high activity and high content of inert component of DCLR may lead to a decrease in the caking property of coal blends. The optimal preparation conditions of DCLR are as follows: liquefaction temperature 430 ℃,carbonization temperature 410 ℃,1% basic iron oxide catalyst. The G index of DCLR is 68,and the adhesion is strong. Thus DCLR is suitable to be used as additive and binder for coal blending and coking. DCLR and QM can partly replace FM by interacting with each other, increase the fluidity of the metaplast, and broaden the melting temperature range of coal blending. A large amounts of gas in the system wallopes the colloidal layer, and squeezes metaplast into the pores of coal particles, so as to obtain high strength coke. In the early stage of coking, the interactions between DCLR and QM have a certain influence on the key process of coking, and increase the degree of anisotropy of coke.

关键词(KeyWords)： 温和液化-炭化耦合;配煤炼焦;冷强度;热强度
integrated mild-liquefaction and carbonization;coal blending for coking;cold strength;thermal strength

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金资助项目(21878096);; 国家重点研发计划资助项目(2018YFB060460)

作者(Author): 陈智辉,吴幼青,吴诗勇,黄胜,陈大波,孙硕,顾嘉乐
CHEN Zhihui,WU Youqing,WU Shiyong,HUANG Sheng,CHEN Dabo,SUN Shuo,GU Jiale

DOI: 10.13226/j.issn.1006-6772.CE21030901

参考文献(References)：

• [1] HIRANO K.Outline of NEDOL coal liquefaction process development(pilot plant program)[J].Fuel Processing Technology,2000,62:109-118.
• [2] KHARE S,DELL A M.An overview of conversion of residues from coal liquefaction processes[J].Canadian Journal of Chemical Engineering,2013,91:324-331.
• [3] WANG Z,XUE W,ZHU J,et al.Study on the stability of hydroliquefaction residue of Shenfu sub-bituminous coal[J].Fuel,2016,181:711-717.
• [4] YANG J,WANG Z,LIU Z,et al.Novel use of residue from direct coal liquefaction process[J].Energy Fuels,2009,23:4717-4722.
• [5] XU L,TANG M,DUAN L,et al.Pyrolysis characteristics and kinetics of residue from China Shenhua industrial direct coal liquefaction plant[J].Thermochim Acta,2014,589:1-10.
• [6] LI X,XUE Y,FENG J,et al.Co-pyrolysis of lignite and Shendong coal direct liquefaction residue[J].Fuel,2015,144:342-348.
• [7] XIAO N,ZHOU Y,QIU J,et al.Preparation of carbon nanofibers/carbon foam monolithic composite from coal liquefaction residue[J].Fuel,2010,89:1169-1171.
• [8] 陈明波，王彬，赵奇，等.煤直接液化残渣焦化特性研究[J].洁净煤技术，2005,10(1):29-33.CHEN Mingbo,WANG Bing,ZHAO Qi,et al.Study on the coking character of coal liquefaction residue[J].Clean Coal Technology.2005,10(1):29-33.
• [9] 武振林.煤液化沥青的制备及其在配煤捣固炼焦中的应用[J].天然气化工(C1化学与化工),2013,38(4):77-79.WU Zhenlin.Preparation of coal liquefied asphalt and its application in coal blending tamping and coking[J].Chemical Engineering of Natural Gas(C1 Chemistry and Chemical Engineering),2013,38(4):77-79.
• [10] 董斌琦，李克健，程时富，等.煤液化沥青的性质及其在配煤炼焦中的应用研究[J].中国煤炭，2014,40(S1):419-424.DONG Bingqi,LI Kejian,CHENG Shifu,et al.Study on the properties of coal liquefied asphalt and its application in coal blending coking[J].China Coal,2014,40(S1):419-424.
• [11] FERNANDEZ A M,BARRIOCANAL C.E?ect of blending carbon-bearing waste with coal on mineralogy and reactivity of cokes[J].Energy Fuels,2014,28:291-298.
• [12] XU J,BAI Z,BAI J,et al.Physico-chemical structure and combustion properties of chars derived from co-pyrolysis of lignite with direct coal liquefaction residue[J].Fuel,2017,187:103-110.
• [13] 吴幼青，吴诗勇，高晋生，等.一种煤温和液化的工艺方法：ZL201310539685.2[P].2014-02-05.WU Youqing,WU Shiyong,GAO Jinsheng,et al.A mild coal liquefaction process:201310539685.2[P].2014-02-05.
• [14] YOU Q,WU S,WU Y,et al.Product distributions and characterizations for integrated mild-liquefaction and carbonization of low rank coals[J].Fuel Processing Technology,2017,156:54-61.
• [15] HUANG H,YUAN X,ZHU H,et al.Comparative studies of thermochemical liquefaction characteristics of microalgae,lignocellulosic biomass and sewage sludge[J].Energy,2013,56:52-60.
• [16] 朱晓苏，王雨，杜淑凤，等.重质液化油延迟焦化的研究[J].煤炭转化，1998,21(2):68-74.ZHU Xiaosu,WANG Yu,DU Shufeng,et al.Study on delayed coking of heavy liquefied oil[J].Coal Conversion,1998,21(2):68-74.
• [17] 宋永辉，马巧娜，贺文晋.煤直接液化残渣热解过程气体产物的析出[J].光谱学与光谱分析，2016,36(7):2017-2021.SONG Yonghui,MA Qiaona,HE Wenjin.Gas product precipitation in the pyrolysis process of coal direct liquefaction residue[J].Spectroscopy and Spectral Analysis,2016,36(7):2017-2021.
• [18] 赵美霞.煤液化中催化剂的研究进展[J].化工管理，2016(6):112-114.ZHAO Meixia.Research progress of catalysts in coal liquefaction[J].Chemical Enterprise Management,2016(6):112-114.
• [19] 黄雍，黄胜，吴诗勇，等.煤液化残渣的理化性质及低温热解行为研究[J].煤炭转化.2015,38(4):43-47.HUANG Yong,HUANG Sheng,WU Shiyong,et al.Study on physicochemical properties and low temperature pyrolysis behavior of coal liquefaction residue[J].Coal Conversion,2015,38(4):43-47.
• [20] 孙任晖，高鹏，芦海云.神东煤与煤液化残渣混合样及共热解半焦黏结性研究[J].煤炭工程，2015,47(11):129-132.SUN Renhui,GAO Peng,LU Haiyun.Study on the bonding property of shendong coal and coal liquefaction residues mixed sample and co-pyrolytic semi-coke[J].Coal Engineering,2015,47(11):129-132.
• [21] 钱虞峰，张卫华，王小四，等.不同产地焦煤的结焦性能差异及原因分析[J].中国煤炭，2018,44(11):92-97.QIAN Yufeng,ZHANG Weihua,WANG Xiaosi,et al.Analysis on the difference of coking properties of coking coal from different producing areas and its causes[J].China Coal,2018,44(11):92-97.